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EXS 50: Experientia Supplementum Vol. 50 Birkhäuser Verlag Basel· Boston· Stuttgart Cadmium in the Environment Edited by Hans Mislin Oscar Ravera 1986 Birkhäuser Verlag Basel' Boston' Stuttgart Parts of this review were published previously in 2 issues of the journal EXPERIENTIA, Vol. 40, No. I, pp. I-52, 1984 and EXPERIENTIA, Vol. 40, No. 2, pp. 117-164, 1984. Library of Congress Cataloging in Publication Data Cadmium in the environment. (Experientia. Supplementum; vol. 50) Parts of this review were published previously in: Experientia ; vo1.40, no.I-2, 1984. Includes bibliographies and index. 1. Cadmium-Toxicology. 2. Cadmium-Environmental aspects. I. Mislin, Hans, 1907- . H. Ravera, O. IH. Series: Experientia. Supplementum; v. 50. [DNLM: 1. Cadmium-adverse effects. 2. Cadmium analysis. 3. Environmental Pollution-analysis. Wl EX23 v. 50 I QV 290 C1241] RA1231.C3C341986 363.7'384 86-8299 ISBN-13: 978-3-0348-7240-9 CIP-Kurztitelaufnahme der Deutschen Bibliothek Cadmium in the environment I ed. by Hans Mislin ; Oscar Ravera. - Basel; Boston; Stuttgart : Birkhäuser, 1986. (Experientia : Supplementum; Vol. 50) ISBN-13: 978-3-0348-7240-9 NE: Mislin, Hans [Hrsg.]; Experientia I Supplementum All rights reserved. No part of this publication may be reproduced, stored in a retrieval system, or transmitted in any form or by any means, e\ectronic, mechanical, photocopying, recording or otherwise, without the prior permission of the copyright owner. © 1986 Birkhäuser Verlag Basel Softcover reprint of the hardcover 1s t edition 1986 ISBN-13: 978-3-0348-7240-9 e-ISBN-13: 978-3-0348-7238-6 DOI: 10.1007/978-3-0348-7238-6 Contents Part I: Cadmium in the Environment I. Thornton: Geochemistry of cadmium. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7 M. Astruc: Evaluation of methods for the speciation of cadmium. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12 C.R. Williams/R.M. Harrison: Cadmium in the atmosphere . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17 W. Salomons/H.N. Kerdijk: 'Cadmium in fresh and estuarine waters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24 L. Mart/H. W. Nürnberg: The distribution of cadmium in the sea. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28 u. Förslner: Cadmium in sediments. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40 c.P.c. Poon: Removal of cadmium from wastewaters. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46 Part 11: Bioaccumulation of Cadmium R.D. Davis: Cadmium in sludges used as fertilizer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55 S. Ray: Bioaccumulation of cadmium in marine organisms ............................................... 65 o. Ravera: Cadmium in freshwater ecosystems. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75 R. Van Bruwaene/R. Kirchmann/R. Impens: Cadmium contamination in agriculture and zootechnology. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87 F.F. Munshower: Pathways and distribution of cadmium in grasslands . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96 R.M. Cox: Contamination and effects of cadmium in native plants. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101 Part 111: Cadmium and Human Health J.c. Sherlock: Cadmium in foods and the diet . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 110 A. Bernard/R. Lauwerys: Cadmium in human population. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 114 Z.A. Shaikh/L.M. Smith: Biological indicators of cadmium exposure and toxicity. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 124 W.H. Hallenbeck: Human health effects of exposure to cadmium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 131 K.J. Yost: Cadmium, the environment and human health . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . 137 7 Part I: Cadmium in the Environment Geochemistry of cadmium by I. Thornton Applied Geochemistry Researc..h Group, Department ofGeology, Imperial College, London SW7 2BP (England) Cadmium, a transition metal, is a member of Group IIB Table 2. Cadmium content of minerals (in J.lg/g, except where noted) of the periodic table, which also includes zinc and mer Mineral Composition Range cury. Pure cadmium is a bluish-white metal but does not Sphalerite (Zn,Cd)S 0.0001-2% occur as such in nature. It was first discovered in 1817 by Greenockite CdS 77.8% a German chemist, F. Stromeyer, as a constituent of the Hawleyite CdS 77.8% Chalcopyrite CuFeS2 < 0.4-110 zinc ore smithsonite (ZnC03). Cadmium is mainly found Marcasite FeS2 < 0.3-< 50 in zinc, lead-zinc and lead-copper-zinc ores, and its con Arsenopyrite FeAsS <5 centration is usually related to their zinc content. It is also Galena PbS < 10.-3000 found in varying amounts as a natural component of the Pyrite FeS2 < 0.06-42 Pyrrhotite Fe(l- Trace surface environment in rocks, overburden and soils, wa x)S Tetrahedrite (Cu,Fe,Zn,Ag)l2SbAs4Sl3 80-2000 ter, air, plant and animal tissues. Its geochemical behav Magnetite Fe304 0-{).31 ior is similar to that of zinc because of the similar electron Cadmium oxide CdO 87.5% Limonite Hydrous iron oxides < 5-1000 structures and ionization potentials of the two elements. Wad and manganese oxides Hydrous manganese oxides < 10-1000 In nature cadmium is nearly always present in the Cd2+ Anglesite PbS04 120-> 1000 oxidation state and occurs as eight stable isotopes as Barite BaS04 < 0.2 shown in table l. 112Cd and ll4Cd are the most common. Anhydrite and gypsum CaS04; CaS04 . 2HP < 0.2 Radioactive isotopes with mass numbers 104, 105, 107, Calcite CaC03 < 1-23 Smithsonite ZnC03 0.1-2.35% 109, 111, 113, 115, 117, 118 and 119 have been made Otavite CdC03 65.18% artificially, of which 113 Cd has the longest half-life of 5.l Pyromorphite PbsCI(P04h < 1-8 years27. Scorodite FeAs04' 2H20 < 1-5.8 Beudantite PbFe3(As04)(S04)(OH)6 100-1000 Apatite Cas(F,CI)(P04h 0.14-D.15 Cadmium in rock forming minerals Bindheimite Pb2Sb206(O,OH) 100-1000 Silicates 0.03-5.8 Cadmium has an ionic radius ofO.97 A, similar to that of (from Boyle and Jonasson\ Ca++ (0.99 A) and Na+ (0.98 A) and could be expected to be found in their minerals. Goldschmidt'O has shown yellow coating on weathering sphalerite (ZnS). Cadmium detectable substitution of cadmium for calcium in bytow is a constituent of several zinc minerals, particularly the nite feldspar of anorthosite and in monoclinic augite phe sulphide, sphalerite which is the principal cadmium bear nocysts of basalts and has also shown crystal structures ing mineral in primary deposits. Cadmium forms an of cadmium oxide and carbonate closely resembling oxide and carbonate under natural conditions of which those of similar calcium compounds. Vinogradov36 com the former is the more common. Both cadmium and zinc ments on the relatively large ionic radius ofCd++ and that are strongly enriched in hydrot hermal rocks and minerals it probably entered into minerals of later crystallization. found at relatively low temperatures. Cadmium is also Cadmium, like zinc, is found in ferro-magnesian miner found in some secondary minerals, particularly smith als. It seldom becomes enriched in igneous rocks24 though sonite (ZnC03) and in hydrous mangane se and iron is present in acid igneous rocks mostly in biotite and in oxides formed in the oxidized zones of zinc deposits. A traces in apatite2S. more comprehensive review of cadmium containing min Cadmium has a markedly chalcophile nature and forms erals is given by Holmes'2, who provides a comprehensive two common sulphides - greenockite and hawleyite (hex listing of the ranges of cadmium concentrations found in agonal and isometric forms respectively of CdS). The sulphide, sulphate, oxide, carbonate, silicate and non former is frequently found under natural conditions as a specific minerals. The cadmium content of the more com mon minerals found in sulphide and other deposits has been tabulated by Boyle and Jonasson7 and this listing is Table 1. Stable isotopes of cadmium with natural abundances reproduced in table 2. The principal cadmium minerals Isotope % formed from the oxidation of primary sphalerite and 106Cd 1.21 other cadmium bearing minerals are greenockite and 108Cd 0.88 hawleyite. Cadmium oxide and octavite are rare. lIoCd 12.39 Waketa and Schmitt27 have also compiled published da ta lllCd 12.75 for the cadmium content of rock-forming minerals, in 112Cd 24.07 113Cd 12.26 cluding those for sphalerites from the United States, the 114Cd 28.86 Soviet Union, Sweden and Vietnam ranging from 500 to 116Cd 7.58 18,500 Ilg/g Cd. 8 Cadmium in rocks Table 4. The cadmium content of some black shales in England and Wales (taken from Holmes!2) The average concentration of cadmium in the earths crust Formation Locality Age Range Mean* has been reported as 0.15 Ilgj g38 and 0.11 Ilgj g5 and in the Lower Worston Bowland Forest upper lithosphere as 0.5 Ilgjg with a zinc:cadmium ratio shale group Lancashire BI-2 < 1-32 4.4 (46) of around 250: 1I O. A similar zinc :cadmium ratio has been Lower Bowland Bowland Forest reported for American magmatic rocks25 and for 'terres shale group Lancashire PI 1-105 16.2 (35) trial' rocks7. The average cadmium content of igneous Lower Bowland Bowland Forest shale group Lancashire P2 1-158 16.5 (20) rocks has been reported as 0.181lgjg with a zinc:cadmium . Upper Bowland Bowland Forest ratio exceeding 400: 125. shale group Lancashire EI 1-219 16.6 (59) Page and Bingham2! have condensed and tabulated data Edale shales North Derbyshire E2 1-39 5.2 (48) for the abundance of cadmium in igneous, sedimentary Edale shales North Derbyshire HI I-50 6.0 (14) Edale shales North Derbyshire H2 < 1-91 14.8 (25) and metamorphic rocks reported by Waketa and Edale shales North Derbyshire RI 1-32 6.0(11) Schmitt37 as shown in table 3. Further tabulated data are Dove shales Southwest Derbyshire E2 < 1-25 6.5 (45) given by Boyle and Jonasson7. There is little difference in Mixon limestone the cadmium content of igneous rocks which rarely con and shales North Staffordshire PI-2 < 1-65 12.8 (31) Onecote sandstone tain more than 1 Ilgjg and usually very much less. For and shales North Staffordshire PI-2 1-39 9.3 (8) example, the mean contents of granites have been vari Onecote sands tone ously reported as ranging from 0.09 to 0.24 Ilgjg and and shales North Staffordshire E2 1-2 1.4 (12) basalts from 0.13 to 0.22Ilgjg. Ofthe sedimentary rocks, Crackington formation Devon/Cornwall HI < 1-5 1.3 (39) bituminous and carbonaceous shales (sometimes referred Crackington to as black shales) may contain abnormally large concen formation Devon/Cornwall RI < 1-4 1.7 (55) trations of cadmium, which may in turn be reflected in Crackington the weathering cycle and provide significant pathways to formation Devon/Cornwall R2 < 1-3 1.5 (29) Coal measures Glamorgan d5 < 1-5 1.0 (9) plants and animals. A detailed study of cadmium in ma Coal measures Chesterfield d5 < 1-3 1.5 (15) rine black shales in Britain has been undertaken by Hol • Number of sampies in parenthesis. mes12, who reports concentrations ranging up to 219 Ilgj g. Data for cadmium in these black shales are summa rized in table 4. Concentrations of cadmium ranging ported as 0.01 to 180 Ilgjg for the U.S.3s, < 0.01 to 22 from 100 to 1000 Ilgjg has been found in the Mansfield copper-shale ('kupferschiefer') in GermanyB, although Ilgjg worldwide5, 0.3 to 2.0 Ilgjg7, up to 0.2llgjg in bitumi nous coals from Australia and 0.1 to 65 Ilgjg in Illinois the accuracy of analysis undertaken at this time may be basin coals28. Concentrations of cadmium in peats have open to question. The mean content of cadmium in bitu been reported as < 1 to 31lgjg (mean 0.25Ilgjg) and up to minous shale has been previously reported as 0.80 Ilgjg37 50 Ilgjg in the ash of enriched bogs24. Cadmium in crude and, in shale 0.22 Ilgjg, sandstone 0.05 Ilgjg and oil ranges widely and in Russia has been reported as limestone 0.028 Ilgjg40. Metamorphic rocks rarely exceed below detection limit to over 1000 Ilgjg23. 1 Ilgjg Cd, though hornfels and skarn may range up to 5 Cadmium has been determined in marine sediments, Ilgjg and schists up to 3 Ilgjg7. ranging from 0.1 to 1.0 Ilgjg in the Atlantic and Pacific The cadmium content of coals ranges widely and is re- oceans20. Oceanic sediments from and flanking the mid Atlantic ridge have been found to contain almost twice the cadmium as those away from ridge systems, with Table 3. Abundance of cadmium in common rocks· average carbonate-free cadmium contents of 0.650 and Rock type Cadmium (Ilg/g) NO.of 0.3351lgjg respectively3. Manganese nodules are enriched Range Mean sampies in cadmium, with a mean content of 8 Ilgjg reported by Igneous Bowen5 (from other published data). Phosphorites may Granite 0.001-{).60 0.12 44 Granodiorite 0.0 I 6-{).1 0 0.07 5 also be enriched, ranging from 0.01 to 25 Ilgjg Cd5. Biotite-granite < 0.05-{).50 9 Quartz monzonite 1.4 -1.8 Pitchstone 0.05-{).34 0.17 24 Cadmium in soils Rhyolite 0.05-{).48 8 Obsidian 0.22-{).29 0.25 2 The main sources of trace metals in unpolluted soils are Andesite 0.017 2 the parent materials from which they are derived. These Syenite 0.04-{).32 0.16 6 materials usually comprise weathered bedrock or over Basalt 0.006-{).6 0.22 39 burden that has been transported by wind, water or gla Gabbro 0.08-{).20 0.11 8 cial activity. 95 percent of the earth's crust is made up of Sedimentary Bituminous shale < 0.3-11 0.80 84 igneous rocks, and 5 % sedimentary rocks, of which Bentonite < 0.3-11 1.4 10 about 80 % are shales, 15 % sandstones and 5 % Marlstone 0.4--10 2.6 8 limestones!9. Sedimentary materials tend to overlie the Shale and claystone < 0.3-8.4 1.0 66 igneous rocks from which they were derived and are thus Limestone 0.035 more common in the surface weathering environment. Metamorphic Soils tend to reflect the chemical composition of the par Eclogite 0.04-{).26 0.11 6 ent materials from which they were derived. Where re Garnet schist 1.0 Grey gneiss 0.12-{).16 0.14 2 sidual soils are formed in situ from the underlying bed • Condensed from data cited by Waketa and Schmitt37. rock, the trace metal content of the soil may be directly 9 Table 5. Amounts ofeadmium, zine and lead in some British soils (Ilg/g, the mobility of cadmium in acidic soils, it has been pro 0-15 em) posed that migration down the soil profile is more likely No. of Cadmium Zine Lead than accumulation at the surface under the influence of sampies humid climatesI3, Redistribution of cadmium and zinc Derbyshire has been clearly shown both in the soil profile and be Miningarea 13 1.1-34 94-8000 230-48000 Control areas 5 0.9-3.8 82-241 69-290 tween neigh~oring soils in a catenary square developed over Carbomferous black shale in Derbyshire, England Shipham Miningarea 12 29-800 2520-62400 720-9600 (table 6), In this instance, cadmium has been leached Control areas 6 2.0-10 208-740 128-344 from i~perfe~tly drained slightly acid soils on the hill top and nelghbonng slopes and accumulated in waterlogged Carboniferous blaek shales org~nic s~ils a~ the base of the slope. Metals are markedly Valley bottoms 7 3.4-24 170-740 120-1480 ennched III sods of several mineralized areas in Britain Hili tops and slopes 17 1.5-5.0 55-460 70-500 with a past history of mining, As shown in table 5 cad (from Marples and ThomtonI5). mium, together with lead and zinc, are present in el;vated concentrations in soils of the historical mining area of Derbyshire where galena (PbS) and sphalerite (ZnS) were related to bedrock geochemistry. However, this relation worked for several hundred years, Mining of zinc in the ship may be modified to varying degrees by pedogenetic processes leading to the mobilization and redistribution form of smithsonite (ZnC03) at Shipham in southwest England has resulted in extremely high concentrations of of elements both within the soil profile and between both cadmium and zinc in soils (table 5) and even soils n~ighboring soils. Although during weathering, cad developed from the host rock, dolomitic conglomerate of miUm goes readily into solution, the main factor deter mining the cadmium content of soil is the chemical com Carboniferous age, contain 10 ~g/g Cd or more and ex tend over some 8 km2. Metals in two soils profiles illus position of the parent rockI3• Kabata-Pendias and Pen trate both a) surface contamination on reclaimed land diasI3, listing the ranges of cadmium contents of surface over the old zinc workings and b) the influence ofunder soils from many parts of the world, report that the aver lying mineralized parent materials (table 7), Further de age contents lie between 0.07 and 1.1 ~g/g and consider tailed studies on the distribution of cadmium and other that all values over 0.5 ~g/g reflect anthropogenic inputs. metals in the soil profiles of this area have been re Anational survey in Japan in 1972 showed a mean con ported1 6,29. centration of cadmium in unpolluted paddy soils of 0.4 ~g/g (n = 2746) and in polluted soils 0.9 ~g/g (n = 300); III areas surrounding zinc mines and smelters the mean Geochemical cycling of cadmium value found in another survey in 1970 was 4.49 ~g/g Cd A detailed description of the sources and cycling of cad (n = 797) with a maximum value in paddy soil of 68.7 mium in the environment falls outside the scope of this ~g/g41. chapter and the subject has been discussed by several The cadmium content of British soils was found to range other authors in this volume. The influence of geo from 0.08 tolO ~g/g (median< 1.0 ~g/g, n = 659)2. How chemical parameters commences during the weathering ever, where cadmium is found in association both with of rocks and mineral deposits containing cadmium. Dur lead-zinc mineralization and with marine black shales soils sometimes contain very much larger concentration~ ing weathering cadmium mainly enters the surface envi ofthe metal, as shown in table 514.15. Cadmium in surface ronment as soluble compounds, mainly as Cd2+, and the most important factors controlling its mobility are pH soils derived from carboniferous black shales in Derby shire ranged from 1.5 to 24 ~g/gI5,16. It has been postu and oxidation potentialI3• It mayaIso form several com lated that the smaller amounts of cadmium found in the plex ions (Cd Cl+, CdOH+, CdHCOJ+, CdCIJ-, CdCI/-, sO,ils co~pared to rocks in some areas underlain by cad Cd(OH)3-) and Cd(OH)42-) and a variety of chelated and organometallic complexes resulting from the decay of miUm-nch black shales in Britain is because of mobiliza tion and leaching of cadmium in the course of soil forma plants and animal matter7, I3. tionI2,15. Ratios ofcadmium in rock:soil of7:1 to 2:1 have Computer-based models using chemical equilibrium pro grams have been deve10ped to predict the chemical spe been shown in several such areas in Britain12, Because of ciation of potentially hazardous trace metals in soils and Table 6. Cd, Zn and Pb in typieal soil profiles overlying earboniferous blaek shale in the vieinity ofTissington, Derbyshire (Marples)14 Cd Zn Pb Table 7. Cd, Zn and Pb in typieal soil profiles in the vicinity of old zine workings at Shipham, Somerset (Marples and Thomtonl5) (Ilg/g, dry soil) Cd Zn Pb a) Pelostagnogley, top of slope (Ilg/g, dry soil) 0-10 cm Clayloam 4 248 316 10-20 cm Clay 4 228 252 a) Brown earth, reclaimed land over zine workings 20-50 cm Clay 3 240 160 0- 2 em Root mat 503 48000 4440 50-75 em Clay 3 356 44 2-20 em Silt loam 559 54000 4600 75-100cm Clay/shale 9 536 100 20-45 em Silt loam 216 22000 1960 b) Earthy eutro-amorphous peat, waterlogged valley bottom b) Brown earth, 300 m from nearest workings 0-10 em Fibrous peat 10 312 204 0- 2 cm Root mat 48 3360 960 40-50 cm Amorphous peat 14 660 414 2-20 cm Silt loam 58 4760 920 70-80 em Peaty clay loam 36 1000 328 20-45 em Silt loam 84 8040 1640 80-90 em Peaty clay loam 52 2280 400 45-60 em Silt loam 188 9720 1560 10 watersI8,26, One such model, GEOCHEM, applied to two Table 8. Cadmium content of natural waters (J.Lg/l (parts per billion)) Californian soils predicted the principal aqueous species Description NO.of Range Mean of cadmium as Cd2+, CdS040 and CdCI+26• This approach sampIes has yet to be applied widely and may prove difficult in Rainwater, snow (virgin areas, high environments where organic compounds are frequent. contents are near mineralised zones) 46 < 0.5 -2.0 < 0.5 Rainwater, snow (urban area, Ottawa) 12 < 0.2 -1.0 0.3 Under strongly oxidizing conditions, cadmium may form Normal stream, river and lake waters 74 < 0.01-5.0 0.3 oxide and carbonate minerals (CdO, CdC01), and under Stream and river waters near cadmium reducing conditions can also utilize H S produced by deposits 10 < 0.01-1000 2 bacteria during the decay of organic residues and precip Oceans and seas 52 0.24-0.48 0.14 Normal groundwaters 22 < 0.01-1.0 0.05 itate as a sulphide. Cadmium precipitated in soils and Groundwaters and mine waters near sediments may be mobilized again by bacteria7, probably polymetallic sulfide deposits 29 Uptol140 in both inorganic and organic forms, and released to soil, As listed by Boyle and Jonasson7 air and water. Most unpolluted waters contain very small amounts of Geochemical maps cadmium and values of less than 1 ng/g have been re ported; however concentrations may exceed 10 ng/g9. The first map to show the distribution of cadmium on a Data compiled by Boyle and Jonasson7 are listed in table regional/national scale was initially published in 197Yl 8; waters in the vicinity of cadmium-bearing mineral de and then in 1978 as part of the Wolfson Geochemical posits may range up to 1000 Jlg/I or more. Inshore waters Atlas of England and Wales19• Based on the analysis of in the U.K. have been shown to range from 0.14 to 4.20 50,000 stream sediment sampIes, maps for 21 elements Jlg Cd/P, reflecting metal-rich inputs from industrial and were presented as smoothed data plotted by computer. old-mining sources. Rivers containing present-day min For cadmium (fig.2) 83 % of the area is covered by the ing effluent and adit drainage from old mines in Corn lowest class interval (less than 1 Jlg/g in the < 204 Jlm wall, southwest England, have been shown to range up to fraction), corresponding to normal base-line concentra 6 Jlg CdW,40· tions in rocks and soils. Anomalous patterns are shown Factors influencing the availability and uptake of cad by the darker areas and indicate three main sources ofthe mium into biological systems are detailed elsewhere in metal: this volume. The principles of environmental geochem 1) Cadmium associated with zinc ores in mineralized istry which govern the chemical characteristics in the areas where past mining and smelting oflead and zinc has surface environment and the complex interactions in the led to contamination of surface drainage and soils. These system rock-water-air-life are outlined by Plant and Rais areas include the mining districts in Derbyshire and we1F2• A generalized geochemical cycle for cadmium has around Shipham, Somerset, mentioned earlier in the been compiled by Boyle and Jonasson7 and is reproduced chapter. in figure 1. 2) Cadmium (usually associated with zinc and/or lead BIOSPHERE DEGRADA TlON Plants ~ Animals I + DEGRADA TlON ABSORPTION AND AND SOLUTION ADSORPTION t I PRECIPIT AT ION HYDROSPHERE PEDOSPHERE ATMOSPHERE Soils PRECIPIT AT lON Water ~ Sediments SOLUTION Glacial Materials t CHEMICAL PRECIPJ AT lON SOLiiON AND AND SEDIMENTATION I OF SOLIDS MECHANICAl I J WEtHERING SOLUTION AND l_ __ ~s!... __ _ MECHANICAl WEATHERING LlTHOSPHERE Rocks CHEMICAl Cadmium· Bearing PRECIPITATION AND . Deposits PRECIPITATION CONSOLIDA TION OF SOLIDS Figure I. Generalized geoehemieal eyde of cadmium (from Boyle and Jonasson7). 11 and other inetals) dispersed by wind and water from Abdullah, M.I., Royle, L.G., and Morris, A. W., Heavy metal con industrial activities, including the world's largest zinc centration in coastal waters. Nature 235 (1972) 158-160. 2 Archer, F.C., Trace elements in soils in England and Wales, in: lead smelter at Avonmouth. Haloes of raised metal val Inorganic Pollution and Agriculture Reference Book 326, pp. 184- ues are also found around some large industrial conurba 190. Ministry of Agriculture Fisheries and Food, H.M.S.O., London tions, particularly Birmingham, England's second largest 1980. city. 3 Aston, S. R, Chester, R., Griffiths, A., and Riley, J. P., Distribution of cadmium in North Atlantic deep sea sediments. Nature 239 (1972) 3) Cadmium derived from the weathering of naturally 393. metal-rich marine black shales of Carboniferous age 4 Aston, S. R., Thornton, 1., Webb, J. S., Purves, J. B., and Milford, which outcrop mainly in parts of central and northwest B. L., Stream sediment composition: an aid to water quality assess England and are referred to in table 5. ment. Water, Air Soil Poil. 3 (1974) 321-325. 5 Bowen, H.J.M., Environmental Chemistry of the Elements. Aca demic Press, London 1979. 6 Boyle, R. W., and Jonasson, I. R, Geochemistry of cadmium. CADMIUM (ppm) Department of Energy, Mines and Resources, Ottawa 1972. < 1 7 Boyle, R W., and Jonasson, I. R, Geochemistry of cadmium, in: Effects of Cadmium in the Canadian Environment, pp. 15-32. Publi 1- 2 ~ 2 -3 ;;;. , cation No. NRCC 16743, National Research Council of Canada, 1979. 3 -4 >4 _ 8 Cissarz, A., Quantitative spectroanalytical investigation of a Mans field Kupferschiefer profile. Chemie der Erde 5 (1930) 48-75. 9 Friberg, L., Piscator, M., Nordberg, G. F., and Kjellstrom, T., Cad mium in the Environment, 2nd edn. CRC Press, Boca Raton, Florida 1974. 10 Goldschmidt, V. M., Geochemistry. Oxford University Press, Ox ford 1958. 11 Goodman, J. G., The dispersion of cadmium, lead and zinc in agri cuItural soils in the vicinity of old zinc mines at Shipham, Somerset. M.Sc. Thesis, University of London, 1979. 12 Holmes, R, The regional distribution of cadmium in England and Wales. Ph.D. Thesis, University ofLondon, 1975. 13 Kabata-Pendias, A., and Pendias, H., Trace Elements in Soils and Plants. CRC Press, Boca Raton, Florida 1984. 14 Marples, A. E., The occurrence and behaviour of cadmium in soils and its uptake by pasture grasses in industrially contaminated and naturally metal-rich environments. Ph.D. Thesis, University of Lon don, 1979. 15 Marples, A. E., and Thornton, 1., The distribution of cadmium derived from geochemical and industrial sources in agricuItural soils and pasture herbage in parts ofBritain, in: CADMIUM 79, pp. 74- 79. Proceedings 2nd Int. Cadmium Conference, Cannes 1979. 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L., Trace elements in soils, in: Chemistry ofthe Soil, 2nd alous patterns of cadmium of 4 flgjg or more occur (com edn. Ed. F. E. Bear. Reinhold Publ. Co., New York 1964. 20 Mullin, J. B., and Riley, J. P., The occurrence ofcadmium in seawater pared to the background of less than I flgjg) extends to and in marine organisms and sediments. J. mar. Res. 15 (1956) some 1200 km2 or 0.33% of the area coveredl5• The re 103-122. sults of several inter-related studies into the sources, dis 21 Page, A. L., and Bingham. F. T., Cadmium residues in the environ persion, distribution and pathways of the metal in the ment. Residue Reviews, vo1.48, pp. 1-43. Ed. F.A. Gunther. Springer-Verlag, New York 1973. rock-soil-plant-animal (including human) system and 22 Plant, J.A ., and Raiswell, R., Principles of environmental geochemi rock-stream sediment-water system have been published stry, in: App1ied Environmental Geochemistry, pp. 1-39. Ed. 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Thornton. Aca centrations of the element resulting from the chemical demic Press, London 1983. 27 Strominger, D., et al., Table of isotopes. Rev. mod. Phys. 30 (1958) composition ofbedrock and overburden, a knowledge of 585. which is essential in order to assess the degree and extent 28 Swaine, D.J., Trace elements in coal, in: Trace Substances in Envi of man-made contamination. ronmental HeaIth, XI, pp. 107-116. Ed. D. D. Hemphill. University

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